CN109134219A - A method of synthesis benzil class derivative - Google Patents
A method of synthesis benzil class derivative Download PDFInfo
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- CN109134219A CN109134219A CN201810907393.2A CN201810907393A CN109134219A CN 109134219 A CN109134219 A CN 109134219A CN 201810907393 A CN201810907393 A CN 201810907393A CN 109134219 A CN109134219 A CN 109134219A
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- C07—ORGANIC CHEMISTRY
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/30—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with halogen containing compounds, e.g. hypohalogenation
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- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B41/00—Formation or introduction of functional groups containing oxygen
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- C07C253/00—Preparation of carboxylic acid nitriles
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- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/313—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of doubly bound oxygen containing functional groups, e.g. carboxyl groups
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
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Abstract
The invention discloses a kind of methods for synthesizing benzil class derivative, and using (diphenyl) acetylene compounds, halogenated ammonium salt or lodine chloride, sulphur source as reactant, after reacting a period of time in a solvent, the benzil class derivative is prepared after purified processing.The method of the invention does not use metallic catalyst and toxic elemental iodine, and reactant used is cheap, and non-toxic and tasteless, operating method is simple, high income, and post-processing is easy, is applicable in industrialized production.
Description
Technical field
The invention belongs to organic synthesis field, in particular to a kind of method for synthesizing benzil class derivative.
Background technique
Benzil and its derivative, can be used for synthetic drug dilantin sodium, insecticide, photoinitiator, auxiliary heat stabilizer,
The corrosion inhibiter of the printing ink and mild steel of packaging, is important organic synthesis intermediate and Organic Chemicals, answers extensively
For industries such as food, medicine, pesticides.
There are many pertinent literature of synthesis benzil and its derivative at present, and may be generally divided into three categories: the first kind is
By benzoin oxidative synthesis benzil and its derivative, this is benzil and its most common synthetic route of derivative；Second class
It is other substances such as talan, aromatic ester is that substrate synthesizes benzil and its derivative, this synthetic technology is not mature enough at present；
It is raw material that third class, which is by tolans, through peroxidating, synthesizes benzil and its derivative, this is that road is commonly synthesized in technique
Line, but yield is not generally high.On the whole, above method prepares benzil and its derivative and there are still some drawbacks, main
To include two aspects: on the one hand consider from the angle of economy and benefit, it is even using effective catalyst catalysis oxidation synthesis benzene
Acyl and its derivative, used catalyst is expensive, environmental pollution is big.Common transition catalyst such as palladium catalyst (Org.Lett.,
2009,11,1841；Eur.J.Org.Chem., 2011,3361), copper catalyst (J.Org.Chem., 2014,79,6279), iron
Catalyst (Tetrahedron, 2006,62,7667；Enthaler, Stephan.ChemCatChem, 2011,3,1929), ruthenium
Catalyst (Adv.Synth.Catal., 2010,352,1424), Au catalyst (Org.Lett., 2011,13,1556), mercury are urged
Agent (Org.Lett., 2014,16,2142) etc..It is worth noting that Adv.Synth.Catal.2010,352,1424-1428
Report that iodine is additives, hydrogen peroxide is oxidant, dioxane makees solvent, ruthenium catalyst catalysis oxidation at 80 DEG C
Tolans prepares benzil, reacts 12 hours, the yield of benzil is 93%.The method makes although catalytic efficiency is very high
It is unfavorable for industrialized production with noble metal catalyst.On the other hand consider from environment and the angle of sustainable development, utilize
No transition metal and inorganic oxidizer oxidation prepare benzil and its derivative, such as oxidant sulfur trioxide, potassium acid sulfate, with
For upper method although high income, the dosage of oxidant is larger, while the tolerance of functional group is insufficient.
CN103274917A discloses a kind of method for catalyzing and synthesizing benzil derivatives from alkali type copper fluoride, with hexichol
Acetylene compound is raw material, using alkali type copper fluoride as catalyst, using the fluoro- Isosorbide-5-Nitrae-diaza of Selectfluor1- chloromethyl -4-
Bicyclic two (tetrafluoro boric acid) salt of [2.2.2] octane is oxidant.In the patent document, use Selectfluor for oxidant,
The oxidant price is more expensive, and about 25 grams/2000 yuan of price (pacifying resistance to Jilin Chemical), be not the common raw material of industry, so its side
Method is not suitable for industrialized production, and Atom economy is not also high.Having used the alkali type copper fluoride containing metallic element is catalyst, reaction
After heavy metal may remain, be unfavorable for the subsequent applications of benzil.
Therefore, a kind of oxidant of Cheap highly effective is developed, can realize highly selective catalysis oxidation two in a mild condition
Phenylacetylene class compound prepares benzil and its method of derivative has great importance.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of method for synthesizing benzil class derivative, has and does not use
The advantages that metallic catalyst, condition are simple, waste discharge is few, functional group tolerance is good, reaction condition temperature.
A method of synthesis benzil class derivative, with (diphenyl) acetylene compounds shown in formula (I), halogenated ammonium salt or
Lodine chloride, sulphur source are reactant, are heated in a solvent, are stirred, and after reacting a period of time, are prepared after purified treatment process
Benzil class derivative shown in formula (II)；
In formula (I) and formula (II), R1Selected from hydrogen, fluorine, chlorine, bromine, iodine, sulfonate group, alkyl, alkoxy, aromatic radical, aldehyde
Base, ester group or carboxyl；R2Selected from hydrogen, fluorine, chlorine, bromine, iodine, sulfonate group, alkyl, alkoxy, aromatic radical, aldehyde radical, ester group or carboxylic
Base.
Preferably, in formula (I) and formula (II), R1It is further excellent selected from hydrogen, fluorine, chlorine, alkyl, alkoxy, aromatic radical
Choosing, the preferred phenyl of aromatic radical, the alkyl of the preferred carbon atom number of alkyl less than 8.
Preferably, R in formula (I) or formula (II)2It is further excellent selected from hydrogen, fluorine, chlorine, alkyl, aromatic radical, aldehyde radical, ester group
Choosing, the preferred phenyl of aromatic radical, the alkyl of the preferred carbon atom number of alkyl less than 8.
Preferably, the halogenated ammonium salt is selected from least one of ammonium iodide, 4- ethyl phosphonium iodide ammonium, ammonium bromide.
Preferably, the sulphur source is selected from elemental sulfur, ammonium sulfide, thiourea cure sodium, potassium sulfide, ehtyl potassium xanthate, xanthan
At least one of sour sodium, further preferably ehtyl potassium xanthate, elemental sulfur, sodium xanthogenate.
Preferably, the molar ratio of the (diphenyl) acetylene compounds and halogenated ammonium salt is 1:0.6~2.5, further excellent
Selecting the molar ratio of the (diphenyl) acetylene compounds and halogenated ammonium salt is 1:1~2.
Preferably, the molar ratio of the (diphenyl) acetylene compounds and sulphur source is 1:0.6~2, further preferred hexichol
The molar ratio of acetylene compound and sulphur source is 1:1.2~2.
Preferably, it is sub- to be selected from water, dichloroethanes, ethyl acetate, chlorobenzene, ethyl alcohol, N- pyrrolidones, dimethyl for the solvent
At least one of sulfone, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, toluene, dimethylbenzene, 1,4- dioxane, into
One step, the solvent is dimethyl sulfoxide and water, and the volume ratio of dimethyl sulfoxide and water is 2~50:1.
Preferably, the volumetric usage of the solvent is calculated as 2 with the amount of the substance of (diphenyl) acetylene compounds shown in formula (I)
~40mL/mmol, the dosage of further preferred solvent are 6~10mL/mmol.
Preferably, the temperature of the heating is 80~150 DEG C, further preferably 100~130 DEG C.
Preferably, the time of the reaction is 6~24 hours, further preferably 10~12 hours.
(volumetric usage of ethyl acetate is with formula (I) institute in order ethyl acetate to be added after reaction for the purification processes process
The amount of the substance of the (diphenyl) acetylene compounds shown is calculated as 5~55mL/mmol) quenching reaction, add saturated salt solution (saturation
The volumetric usage of saline solution is calculated as 4~30mL/mmol with the amount of the substance of (diphenyl) acetylene compounds shown in formula (I)), it washes
It washs, separates organic phase, water phase uses ethyl acetate again, and (volumetric usage of ethyl acetate is with diphenyl acetylene class chemical combination shown in formula (I)
The amount of substance be calculated as 4~30mL/mmol) extraction 3~5 times, merge organic phase, it is dry to be added anhydrous sodium sulfate, steams through decompression
Solvent is removed in distillation, then chromatographs to obtain the benzil class derivative through column.
In reaction of the present invention, halogenated ammonium salt or lodine chloride and sulphur source can not only serve as the effect of catalyst together, and
And when reaction temperature reaches 80~150 DEG C, halogenated ammonium salt or lodine chloride and sulphur source, which react to generate, has oxidation susceptibility
Substance serves as the effect of oxidant in entire reaction process, (diphenyl) acetylene compounds shown in formula (I) can be aoxidized an accepted way of doing sth
(II) benzil class derivative shown in.
The present invention has the beneficial effect that:
1. the present invention does not use metallic catalyst and toxic elemental iodine compared with previous methods.
2. ammonium iodide used in the present invention and ehtyl potassium xanthate are cheap, non-toxic and tasteless, post-processing is easy, is applicable in
Industrialized production.
3. operation of the present invention method is simple, high income.
Specific embodiment
In order to allow those skilled in the art's more clearly the technical program, it is exemplified below some embodiments.
Embodiment 1
This is the synthesis of benzil.
(a) reaction tube is taken, tolans 89mmg (0.50mmol), ehtyl potassium xanthate 96mmg are separately added into
(0.60mmol), ammonium iodide 145mmg (1.00mmol), dimethyl sulfoxide 2mL, water 1mL are stirred to react 12 hours at 130 DEG C,
Reaction terminates that ethyl acetate 10mL quenching reaction is added, and 5mL saturated common salt water washing is added, separates organic phase, water phase uses second again
Acetoacetic ester extracts 3 times, and each ethyl acetate dosage is 5mL, merges organic phase, anhydrous sodium sulfate drying is added, through being evaporated under reduced pressure
Solvent is removed, then chromatographs to obtain pure product through column, the yield of product is 93%.
(b) reaction tube is taken, tolans 89mmg (0.50mmol), ehtyl potassium xanthate 160mmg are separately added into
(1.00mmol), ammonium iodide 145mmg (1.00mmol), dimethyl sulfoxide 2mL, water 1mL are stirred to react 12 hours at 130 DEG C,
Reaction terminates that ethyl acetate 10mL quenching reaction is added, and 5mL saturated common salt water washing is added, separates organic phase, water phase uses second again
Acetoacetic ester extracts 3 times (each ethyl acetate dosage is 5mL) and merges organic phase, anhydrous sodium sulfate drying is added, through being evaporated under reduced pressure
Solvent is removed, then chromatographs to obtain target product benzil, yield 87% through column.
(c) reaction tube is taken, tolans 89mmg (0.50mmol), ehtyl potassium xanthate 96mmg are separately added into
(0.60mmol), ammonium iodide 145mmg (1.00mmol), dimethyl sulfoxide 2mL, water 1mL.At 120 DEG C, it is stirred to react 18 hours,
Reaction terminates that ethyl acetate 10mL quenching reaction is added, and 5mL saturated common salt water washing is added, separates organic phase, water phase uses second again
Acetoacetic ester extracts 5 times (each ethyl acetate dosage is 5mL) and merges organic phase, anhydrous sodium sulfate drying is added, through being evaporated under reduced pressure
Solvent is removed, then chromatographs to obtain target product benzil, yield 86% through column.
Characterize data is1H NMR (400MHz, CDCl3) δ 7.86 (d, J=7.8Hz, 4H), 7.53 (t, J=7.4Hz,
2H), 7.39 (t, J=7.7Hz, 4H)；13C NMR(100MHz,CDCl3)δ194.50(2C),134.82(2C),132.89
(2C),129.79(4C),128.94(4C)；MS(EI,70eV)m/z:210,105,77.
Embodiment 2
This example is the synthesis of 1- (4- methoxyphenyl) -2- vinylbenzene -1,2- diketone.
In reaction tube, it is separately added into 1- methoxyl group -4- (phenylacetylene base) benzene 104mmg (0.50mmol), ethyl xanthan
Sour potassium 96mmg (0.60mmol), ammonium iodide 145mmg (1.00mmol), dimethyl sulfoxide 2mL, water 1mL.It is stirred at 130 DEG C anti-
It answers 12 hours.Reaction terminates that ethyl acetate 10mL quenching reaction is added, and 5mL saturated common salt water washing is added, separates organic phase, water
3 times (each ethyl acetate dosage is 5mL) are mutually extracted with ethyl acetate again and merges organic phase, anhydrous sodium sulfate drying, warp is added
Vacuum distillation removes solvent, then obtains target product 1- (4- methoxyphenyl) -2- vinylbenzene -1,2- bis- through column chromatography for separation
Ketone, yield 92%.
Characterize data is1H NMR (400MHz, CDCl3) δ 7.96 (t, J=8.7Hz, 1H), 7.64 (t, J=7.4Hz,
0H), 7.50 (t, J=7.7Hz, 1H), 6.97 (d, J=8.8Hz, 1H), 3.88 (s, 3H)；13C NMR(100MHz,CDCl3)δ
194.83,193.14,164.97,134.68,133.16,132.35,129.86,128.92,126.05,114.34,55.62；
MS(EI,70eV)m/z:270,135,77。
Embodiment 3
This example is the synthesis of 1- (4- bromophenyl) -2- vinylbenzene -1,2- diketone.
In reaction tube, it is separately added into 1- bromo- 4- (phenylacetylene base) benzene 128mmg (0.51mmol), ehtyl potassium xanthate
96mmg (0.60mmol), ammonium iodide 145mmg (1.00mmol), dimethyl sulfoxide 2mL, water 1mL.12 are stirred to react at 130 DEG C
Hour.Reaction terminates that ethyl acetate 10mL quenching reaction is added, and 6mL saturated common salt water washing is added, separates organic phase, water phase is again
It is extracted with ethyl acetate 3 times (each ethyl acetate dosage is 6mL) and merges organic phase, anhydrous sodium sulfate drying is added, through depressurizing
Solvent is distilled off, then obtains target product 1- (4- bromophenyl) -2- vinylbenzene -1,2- diketone through column chromatography for separation, yield is
82%.
Characterize data is1H NMR (400MHz, CDCl3) δ 7.96 (d, J=7.8Hz, 2H), 7.84 (d, J=8.5Hz,
2H), 7.67 (t, J=7.7Hz, 3H), 7.52 (t, J=7.7Hz, 2H)；13C NMR(100MHz,CDCl3)δ193.81,
193.24,135.05,132.74,132.41,131.72,131.21,130.48,129.92,129.06；MS(EI,70eV)m/
z:290,115,113,105。
Embodiment 4
This example is the synthesis of 1- (4- fluorophenyl) -2- vinylbenzene -1,2- diketone.
In reaction tube, it is separately added into 1- fluoro- 4- (phenylacetylene base) benzene 98mmg (0.52mmol), ehtyl potassium xanthate
96mmg (0.60mmol), ammonium iodide 145mmg (1.00mmol), dimethyl sulfoxide 2mL, water 1mL.12 are stirred to react at 130 DEG C
Hour.Reaction terminates that ethyl acetate 10mL quenching reaction is added, and 5mL saturated common salt water washing is added, separates organic phase, water phase is again
It is extracted with ethyl acetate 3 times (each ethyl acetate dosage is 5mL) and merges organic phase, anhydrous sodium sulfate drying is added, through depressurizing
Solvent is distilled off, then obtains target product 1- (4- fluorophenyl) -2- vinylbenzene -1,2- diketone through column chromatography for separation, yield is
86%.
Characterize data is1H NMR (400MHz, CDCl3) δ 8.08-7.91 (m, 4H), 7.67 (t, J=7.4Hz, 1H),
7.52 (t, J=7.7Hz, 2H), 7.19 (t, J=8.5Hz, 2H)；13C NMR(100MHz,CDCl3)δ194.04,192.70,
168.04,165.48,134.98,132.82,132.76,132.66,129.91,129.49,129.47,129.04,116.48,
116.26；MS(EI,70eV)m/z:228,123,105,95,77.
Embodiment 5
This example is the synthesis of 1- (3- fluorophenyl) -2- vinylbenzene -1,2- diketone.
In reaction tube, it is separately added into 1- fluoro- 3- (phenylacetylene base) benzene 98mmg (0.52mmol), ehtyl potassium xanthate
96mmg (0.60mmol), ammonium iodide 145mmg (1.00mmol), dimethyl sulfoxide 2mL, water 1mL.12 are stirred to react at 130 DEG C
Hour.Reaction terminates that ethyl acetate 10mL quenching reaction is added, and 5mL saturated common salt water washing is added, separates organic phase, water phase is again
It is extracted with ethyl acetate 3 times (each ethyl acetate dosage is 5mL) and merges organic phase, anhydrous sodium sulfate drying is added, through depressurizing
Solvent is distilled off, then obtains target product 1- (3- fluorophenyl) -2- vinylbenzene -1,2- diketone through column chromatography for separation, yield is
86%.
Characterize data is1H NMR (400MHz, CDCl3) δ 7.96 (d, J=7.6Hz, 2H), 7.79-7.60 (m, 2H),
7.57-7.42 (m, 3H), 7.34 (td, J=8.2,2.5Hz, 1H)；13C NMR(100MHz,CDCl3)δ193.62,192.97,
192.95,163.99,161.51,135.03,134.89,134.83,132.60,130.79,130.71,129.84,129.01,
125.92,125.89,122.02,121.81,116.07,115.85；MS(EI,70eV)m/z:228,123,105,95,77.
Embodiment 6
This example is the synthesis of 1- (4- xenyl) -2- vinylbenzene -1,2- diketone.
In reaction tube, it is separately added into 4- (phenylacetylene base) -1,1- biphenyl 127mmg (0.50mmol), ehtyl potassium xanthate
96mmg (0.60mmol), ammonium iodide 145mmg (1.00mmol), dimethyl sulfoxide 2mL, water 1mL.12 are stirred to react at 130 DEG C
Hour.Reaction terminates that ethyl acetate 10mL quenching reaction is added, and 5mL saturated common salt water washing is added, separates organic phase, water phase is again
It is extracted with ethyl acetate 3 times (each ethyl acetate dosage is 5mL) and merges organic phase, anhydrous sodium sulfate drying is added, through depressurizing
Solvent is distilled off, then obtains target product 1- (4- xenyl) -2- vinylbenzene -1,2- diketone through column chromatography for separation, yield is
83%.
Characterize data is1H NMR (400MHz, CDCl3) δ 8.03 (dd, J=17.4,7.9Hz, 4H), 7.74 (d, J=
8.3Hz, 2H), 7.71-7.60 (m, 3H), 7.59-7.45 (m, 4H), 7.42 (dd, J=8.3,6.2Hz, 1H)；13C NMR
(100MHz,CDCl3)δ194.54,194.13,147.61,139.48,134.87,133.03,131.68,130.48,
129.94,129.03,128.63,127.64,127.34；MS(EI,70eV)m/z:286,181,105,77.
Embodiment 7
This example is the synthesis of 4- (2- oxo -2- phenyl acetyl) benzyl cyanogen.
In reaction tube, it is separately added into 4- (phenylacetylene base) benzyl cyanogen 102mmg (0.47mmol), ehtyl potassium xanthate 96mmg
(0.60mmol), ammonium iodide 145mmg (1.00mmol), dimethyl sulfoxide 2mL, water 1mL.It is stirred to react at 130 DEG C 12 hours.
Reaction terminates that ethyl acetate 10mL quenching reaction is added, and 5mL saturated common salt water washing is added, separates organic phase, water phase uses second again
Acetoacetic ester extracts 3 times (each ethyl acetate dosage is 5mL) and merges organic phase, anhydrous sodium sulfate drying is added, through being evaporated under reduced pressure
Solvent is removed, then obtains target product 4- (2- oxo -2- phenyl acetyl) benzyl cyanogen, yield 85% through column chromatography for separation.
Characterize data is1H NMR(600MHz,CDCl3)δ8.11–8.05(m,2H),8.00–7.92(m,2H),7.85–
7.79(m,2H),7.72–7.66(m,1H),7.58–7.50(m,2H)；13C NMR(150MHz,CDCl3)δ192.96,
192.37,135.79,135.36,132.70(2C),132.36,130.15(2C),129.96(2C),129.15(2C),
117.82,117.53；MS(EI,70eV)m/z:235,130,105,77.
Embodiment 8
This example is the synthesis of 4- (2- oxo -2- phenyl acetyl) benzaldehyde.
In reaction tube, it is separately added into 4- (phenylacetylene base) benzaldehyde 103mmg (0.47mmol), ehtyl potassium xanthate
96mmg (0.60mmol), ammonium iodide 145mmg (1.00mmol), dimethyl sulfoxide 2mL, water 1mL.12 are stirred to react at 130 DEG C
Hour.Reaction terminates that ethyl acetate 10mL quenching reaction is added, and 5mL saturated common salt water washing is added, separates organic phase, water phase is again
It is extracted with ethyl acetate 3 times (each ethyl acetate dosage is 5mL) and merges organic phase, anhydrous sodium sulfate drying is added, through depressurizing
Solvent is distilled off, then obtains target product 4- (2- oxo -2- phenyl acetyl) benzaldehyde through column chromatography for separation, yield is
83%.
Characterize data is1H NMR (600MHz, CDCl3) δ 10.13 (s, 1H), 8.14 (d, J=8.3Hz, 2H), 8.07-
8.01 (m, 2H), 7.99 (dd, J=8.3,1.1Hz, 2H), 7.73-7.64 (m, 1H), 7.54 (t, J=7.9Hz, 2H)；13C
NMR(150MHz,CDCl3)δ193.56,193.43,191.31,140.02,137.03,135.25,132.59,130.41
(2C),129.99(2C),129.96(2C),129.15(2C)；MS(EI,70eV)m/z:238,133,105.
Embodiment 9
This example is the synthesis of 4- (2- oxo -2- phenyl acetyl) methyl benzoate.
In reaction tube, it is separately added into 4- (phenylacetylene base) methyl benzoate 118mmg (0.50mmol), sulphur 64mmg
(2.00mmol), 4- ethyl phosphonium iodide ammonium 514.3mmg (2.00mmol), dimethyl sulfoxide 19.60mL, water 0.40mL.At 150 DEG C
It is stirred to react 6 hours.Reaction terminates that ethyl acetate 5mL quenching reaction is added, and 2mL saturated common salt water washing is added, separates organic
3 times (each ethyl acetate dosage is 15mL) are extracted with ethyl acetate again and merges organic phase for phase, water phase, and it is dry that anhydrous sodium sulfate is added
It is dry, solvent is removed through vacuum distillation, then obtain target product 4- (2- oxo -2- phenyl acetyl) benzoic acid through column chromatography for separation
Methyl esters, yield 84%.
Characterize data is1H NMR (600MHz, CDCl3) δ 8.17 (d, J=8.3Hz, 2H), 8.04 (d, J=8.3Hz,
2H), 7.98 (d, J=7.4Hz, 2H), 7.68 (t, J=7.4Hz, 1H), 7.53 (t, J=7.8Hz, 2H), 3.96 (s, 3H)；13C
NMR(150MHz,CDCl3)δ193.79,193.66,165.89,136.04,135.32,135.15,132.70,130.09
(2C),129.98(2C),129.79(2C),129.11(2C),52.63；MS(EI,70eV)m/z:268,163,105,77.
Embodiment 10
This example is the synthesis of 4- (2- oxo -2- phenyl acetyl) ethyl benzoate.
In reaction tube, it is separately added into 4- (phenylacetylene base) ethyl benzoate 125mmg (0.50mmol), ammonium sulfide 43mmg
(0.50mmol), lodine chloride 162.30mmg (1.00mmol), N- pyrrolidones 5mL.It is stirred to react at 100 DEG C 10 hours.Reaction
Terminate that ethyl acetate 10mL quenching reaction is added, 7mL saturated common salt water washing is added, separates organic phase, water phase uses acetic acid second again
Ester extracts 3 times (each ethyl acetate dosage is 7mL) and merges organic phase, and anhydrous sodium sulfate drying is added, removes through vacuum distillation
Solvent, then target product 4- (2- oxo -2- phenyl acetyl) ethyl benzoate, yield 87% are obtained through column chromatography for separation.
Characterize data is1H NMR (600MHz, CDCl3) δ 8.16 (d, J=8.4Hz, 2H), 8.04 (d, J=8.4Hz,
2H), 7.97 (d, J=7.3Hz, 2H), 7.68 (t, J=7.4Hz, 1H), 7.53 (t, J=7.8Hz, 2H), 4.41 (q, J=
7.2Hz, 2H), 1.41 (t, J=7.2Hz, 3H)；13C NMR(150MHz,CDCl3)δ193.82,193.72,165.39,
135.95,135.69,135.11,132.71,130.04(2C),129.95(2C),129.73(2C),129.09(2C),
61.65,14.22；MS(EI,70eV)m/z:282,177,105,77.
Embodiment 11
This example is the synthesis of 1,2-, bis--meta position toluene vinylbenzene -1,2- diketone.
In reaction tube, it is separately added into 1,2- bis--tolacetylene 103mmg (0.50mmol), ehtyl potassium xanthate
96mmg (0.60mmol), ammonium iodide 145mmg (1.00mmol), dimethyl sulfoxide 2mL, water 1mL.12 are stirred to react at 130 DEG C
Hour.Reaction terminates that ethyl acetate 10mL quenching reaction is added, and 5mL saturated common salt water washing is added, separates organic phase, water phase is again
It is extracted with ethyl acetate 3 times (each ethyl acetate dosage is 5mL) and merges organic phase, anhydrous sodium sulfate drying is added, through depressurizing
Solvent is distilled off, then obtains target product 1,2- bis--meta position toluene vinylbenzene -1,2- diketone through column chromatography for separation, yield is
95%.
Characterize data is1H NMR (400MHz, CDCl3) δ 7.86 (d, J=8.0Hz, 4H), 7.28 (t, J=8.0Hz,
4H),2.42(s,6H)；13C NMR(100MHz,CDCl3)δ194.43,146.01,130.63,129.92,129.63,21.82；
MS(EI,70eV)m/z:238,119,91,65。
Embodiment 12
This example be 1,2- it is bis--synthesis of (4- (dimethylamino) phenyl) ethane -1,2- diketone.
In reaction tube, it is separately added into bis- (n,N-Dimethylaniline) 132mmg of 4,4- (1,2- acetenyl)
(0.50mmol), ehtyl potassium xanthate 96mmg (0.60mmol), ammonium iodide 145mmg (1.00mmol), dimethyl sulfoxide 2mL,
Water 1mL.It is stirred to react at 130 DEG C 12 hours.Reaction terminates that ethyl acetate 10mL quenching reaction is added, and 5mL saturated common salt is added
Water washing, separates organic phase, and 3 times (each ethyl acetate dosage is 5mL) are extracted with ethyl acetate again and merges organic phase, adds for water phase
It is dry to enter anhydrous sodium sulfate, removes solvent through vacuum distillation, then obtains target product 1 through column chromatography for separation, 2- is bis--(4- (diformazan
Base amino) phenyl) ethane -1,2- diketone, yield 91%.
Characterize data is1H NMR (600MHz, CDCl3) δ 7.84 (d, J=8.7Hz, 4H), 6.63 (d, J=8.8Hz,
4H),3.05(s,12H)；13C NMR(150MHz,CDCl3)δ193.9(2C),154.1(2C),132.1(4C),121.5(2C),
110.8(4C),39.95(4C)；MS (EI, 70eV) m/z (%): 296,148,105,77.
Embodiment 13
This example is 1- (4- chlorphenyl) -2- to toluene ethane 1, the synthesis of 2- diketone.
In reaction tube, it is separately added into the chloro- 4- of 1- (p-methylphenyl acetenyl) benzene 226mmg (1.00mmol), ethyl xanthan
Sour potassium 96mmg (0.60mmol), ammonium iodide 145mmg (1.00mmol), dimethyl sulfoxide 2mL, water 1mL.It is stirred at 130 DEG C anti-
It answers 12 hours.Reaction terminates that ethyl acetate 10mL quenching reaction is added, and 5mL saturated common salt water washing is added, separates organic phase, water
3 times (each ethyl acetate dosage is 5mL) are mutually extracted with ethyl acetate again and merges organic phase, anhydrous sodium sulfate drying, warp is added
Vacuum distillation removes solvent, then obtains target product 1- (4- chlorphenyl) -2- to toluene ethane 1 through column chromatography for separation, 2- diketone,
Yield 80%.
Characterize data is1H NMR (400MHz, CDCl3) δ 7.91 (d, J=8.4Hz, 2H), 7.85 (d, J=8.1Hz,
2H), 7.47 (d, J=8.4Hz, 2H), 7.31 (d, J=8.0Hz, 2H), 2.43 (s, 2H)；13C NMR(100MHz,CDCl3)δ
193.54,193.20,146.39,141.40,131.42,131.15,130.33,130.00,129.75,129.33,21.88；
MS(EI,70eV)m/z:258,139,119,91。
Embodiment 14
This example is the synthesis of 1- (the fluoro- 4- tolyl of 2-) p- tolyl ethane -1,2- diketone of -2-.
In reaction tube, it is separately added into 1- fluoro- 3- methyl -5- (p-methylphenyl acetenyl) benzene 112mmg (0.50mmol),
Sodium xanthogenate 86.5mmg (0.60mmol), ammonium bromide 80mmg (1.00mmol), dichloroethanes 4mL.12 are stirred to react at 80 DEG C
Hour, reaction terminates that ethyl acetate 10mL quenching reaction is added, and 6mL saturated common salt water washing is added, separates organic phase, water phase is again
It is extracted with ethyl acetate 4 times (each ethyl acetate dosage is 6mL) and merges organic phase, anhydrous sodium sulfate drying is added, through depressurizing
Solvent is distilled off, then obtains target product 1- (the fluoro- 4- tolyl of 2-) p- tolyl ethane -1,2- of -2- through column chromatography for separation
Diketone, yield 83%.
Characterize data is1H NMR (400MHz, CDCl3) δ 7.93 (t, J=7.7Hz, 1H), 7.85 (d, J=7.9Hz,
2H), 7.31 (d, J=7.9Hz, 2H), 7.13 (d, J=8.0Hz, 1H), 6.92 (d, J=11.5Hz, 1H), 2.43 (s, 3H),
2.42(s,2H)；13C NMR(100MHz,CDCl3)δ193.08,191.84,164.17,161.60,149.02,148.93,
145.81,130.57,130.55,129.90,129.70,129.65,125.85,125.82,119.82,119.71,117.04,
116.83,21.87,21.81；MS(EI,70eV)m/z:256,137,119,109,91.
Embodiment 15
This example is the synthesis of 1- (4- chlorobenzene) -2- (4- toluene fluoride base) ethane -1,2- diketone.
In reaction tube, it is separately added into the fluoro- 4- of 1- ((4- fluorophenyl) acetenyl) benzene 115mmg (0.54mmol), ethyl is yellow
Ortho acid potassium 96mmg (0.60mmol), ammonium iodide 145mmg (1.00mmol), dimethyl sulfoxide 2mL, water 1mL.It is stirred at 130 DEG C
Reaction 12 hours.Reaction terminates that ethyl acetate 10mL quenching reaction is added, and 5mL saturated common salt water washing is added, separates organic phase,
3 times (each ethyl acetate dosage is 5mL) are extracted with ethyl acetate again and merges organic phase for water phase, and anhydrous sodium sulfate drying is added,
Solvent is removed through vacuum distillation, then obtains target product 1- (4- chlorobenzene) -2- (4- toluene fluoride base) ethane -1 through column chromatography for separation,
2- diketone, yield 84%.
Characterize data is1H NMR (400MHz, CDCl3) δ 8.01 (dd, J=8.3,5.6Hz, 2H), 7.92 (d, J=
8.3Hz, 2H), 7.49 (d, J=8.3Hz, 2H), 7.19 (t, J=8.4Hz, 2H)；13C NMR(100MHz,CDCl3)δ
192.51,191.98,168.14,165.57,141.71,132.83,132.73,131.23,131.18,129.45,129.28,
129.25,116.55,116.33；MS(EI,70eV)m/z:262,139,123,111,95.
Embodiment 16
This example is the synthesis of 1- (4- chlorphenyl) -2- (2- thienyl) ethane -1,2- diketone.
In reaction tube, it is separately added into 2- ((4- chlorphenyl) acetenyl) thiophene 109mmg (0.50mmol), ethyl xanthan
Sour potassium 96mmg (0.60mmol), ammonium iodide 145mmg (1.00mmol), dimethyl sulfoxide 2mL, water 1mL.It is stirred at 130 DEG C anti-
It answers 12 hours.Reaction terminates that ethyl acetate 10mL quenching reaction is added, and 5mL saturated common salt water washing is added, separates organic phase, water
3 times (each ethyl acetate dosage is 5mL) are mutually extracted with ethyl acetate again and merges organic phase, anhydrous sodium sulfate drying, warp is added
Vacuum distillation removes solvent, then obtains target product 1- (4- chlorphenyl) -2- (2- thienyl) ethane -1,2- through column chromatography for separation
Diketone, yield 84%.
Characterize data is1H NMR (400MHz, CDCl3) δ 7.99 (d, J=8.6Hz, 2H), 7.89-7.79 (m, 2H),
7.48 (d, J=8.6Hz, 2H), 7.18 (dd, J=4.7,4.1Hz, 1H)；13C NMR(100MHz,CDCl3)δ190.42,
184.63,141.45,139.46,137.15,136.83,131.51,130.92,129.22,128.80；MS(EI,70eV)m/
z:250,139,111,75。
Embodiment 17
This example is the synthesis of 1- (2- thienyl) 2- (3- thienyl) ethane -1,2- diketone.
In reaction tube, it is separately added into 2- (thiophene -2- acetenyl) thiophene 95mmg (0.50mmol), ehtyl potassium xanthate
96mmg (1.00mmol), ammonium iodide 145mmg (1.00mmol), dimethyl sulfoxide 2mL, water 1mL.12 are stirred to react at 130 DEG C
Hour.Reaction terminates that ethyl acetate 10mL quenching reaction is added, and 5mL saturated common salt water washing is added, separates organic phase, water phase is again
It is extracted with ethyl acetate 3 times (each ethyl acetate dosage is 5mL) and merges organic phase, anhydrous sodium sulfate drying is added, through depressurizing
Solvent is distilled off, then obtains target product 1- (2- thienyl) 2- (3- thienyl) ethane -1,2- diketone through column chromatography for separation,
Yield is 85%.
Characterize data is1H NMR (400MHz, CDCl3) δ 8.48-8.41 (m, 1H), 7.96 (d, J=3.8Hz, 1H),
7.82 (d, J=4.9Hz, 1H), 7.71 (d, J=5.1Hz, 1H), 7.38 (dd, J=5.0,2.9Hz, 1H), 7.19 (t, J=
4.4Hz,1H)；13C NMR(100MHz,CDCl3)δ184.30,183.78,139.08,137.68,137.29,137.07,
136.91,128.64,127.64,126.75；MS(EI,70eV)m/z:222,111,83.
Embodiment 18
This example is the synthesis of 1- [4- (2 oxo -2- phenylacetylene base) phenyl] -2- vinylbenzene -1,2- diketone.
(a) in reaction tube, be separately added into 1-4- it is bis--(phenylene-ethynylene) benzene 139mmg (0.50mmol), ethyl xanthan
Sour potassium 96mmg (0.60mmol), ammonium iodide 145mmg (1.00mmol), dimethyl sulfoxide 2mL, water 1mL.It is stirred at 130 DEG C anti-
It answers 12 hours.Reaction terminates that ethyl acetate 10mL quenching reaction is added, and 5mL saturated common salt water washing is added, separates organic phase, water
3 times (each ethyl acetate dosage is 5mL) are mutually extracted with ethyl acetate again and merges organic phase, anhydrous sodium sulfate drying, warp is added
Vacuum distillation removes solvent, then obtains target product 1- [4- (2 oxo -2- phenylacetylene base) phenyl] -2- benzene through column chromatography for separation
Ethane -1,2- diketone, yield 89%.
(b) in reaction tube, be separately added into 1-4- it is bis--(phenylene-ethynylene) benzene 139mmg (0.50mmol), ethyl xanthan
Sour potassium 96mmg (0.60mmol), ammonium iodide 145mmg (1.00mmol), dimethyl sulfoxide 2mL, water 1mL.It is stirred at 100 DEG C anti-
It answers 10 hours.Reaction terminates that ethyl acetate 10mL quenching reaction is added, and 5mL saturated common salt water washing is added, separates organic phase, water
4 times (each ethyl acetate dosage is 5mL) are mutually extracted with ethyl acetate again and merges organic phase, anhydrous sodium sulfate drying, warp is added
Vacuum distillation removes solvent, then obtains target product 1- [4- (2 oxo -2- phenylacetylene base) phenyl] -2- benzene through column chromatography for separation
Ethane -1,2- diketone, yield 85%.
Characterize data is1H NMR (400MHz, CDCl3) δ 8.11 (s, 4H), 7.97 (d, J=8.0Hz, 4H), 7.69 (t,
J=7.3Hz, 3H), 7.54 (t, J=7.7Hz, 4H)；13C NMR(100MHz,CDCl3)δ193.43,193.27,137.13,
135.26,132.57,130.26,129.99,129.16；MS(EI,70eV)m/z:342,237,105.
Claims (10)
1. it is a kind of synthesize benzil class derivative method, which is characterized in that with (diphenyl) acetylene compounds shown in formula (I),
Halogenated ammonium salt or lodine chloride, sulphur source are that formula is prepared after purified processing after reacting a period of time in a solvent in reactant
(II) benzil class derivative shown in；
In formula (I) and formula (II), R1Selected from hydrogen, fluorine, chlorine, bromine, iodine, sulfonate group, alkyl, alkoxy, aromatic radical, aldehyde radical, ester group
Or carboxyl；
In formula (I) and formula (II), R2Selected from hydrogen, fluorine, chlorine, bromine, iodine, sulfonate group, alkyl, alkoxy, aromatic radical, aldehyde radical, ester group
Or carboxyl.
2. the method for synthesis benzil class derivative according to claim 1, which is characterized in that halogenated ammonium salt is selected from iodate
At least one of ammonium, 4- ethyl phosphonium iodide ammonium and ammonium bromide.
3. it is according to claim 1 synthesis benzil class derivative method, which is characterized in that sulphur source be selected from elemental sulfur,
At least one of ammonium sulfide, thiocarbamide, vulcanized sodium, potassium sulfide, potassium xanthate and sodium xanthogenate.
4. the method for synthesis benzil class derivative according to claim 1, which is characterized in that (diphenyl) acetylene compounds
It is 1:0.6~2.5 with the molar ratio of halogenated ammonium salt or lodine chloride.
5. the method for synthesis benzil class derivative according to claim 1, which is characterized in that (diphenyl) acetylene compounds
Molar ratio with sulphur source is 1:0.6~2.
6. the method for synthesis benzil class derivative according to claim 1, which is characterized in that solvent is selected from water, dichloro
Ethane, ethyl acetate, chlorobenzene, ethyl alcohol, N- pyrrolidones, dimethyl sulfoxide, N,N-dimethylformamide, N, N- dimethylacetamide
At least one of amine, toluene, dimethylbenzene and 1,4- dioxane.
7. it is according to claim 1 synthesis benzil class derivative method, which is characterized in that the volumetric usage of solvent with
The amount of the substance of (diphenyl) acetylene compounds shown in formula (I) is calculated as 2~40mL/mmol.
8. the method for synthesis benzil class derivative according to claim 1 or 6, which is characterized in that the solvent is selected from
Dimethyl sulfoxide and water, and the volume ratio of dimethyl sulfoxide and water is 2~50:1.
9. it is according to claim 1 synthesis benzil class derivative method, which is characterized in that the temperature of reaction be 80~
150 DEG C, the time of reaction is 6~24 hours.
10. the method for synthesis benzil class derivative according to claim 1, which is characterized in that purification processes are reaction
After be added ethyl acetate quenching reaction, by washing, separate organic phase, water phase is extracted with ethyl acetate again, merge it is organic
Phase, then be dried, be evaporated under reduced pressure removing solvent, then chromatograph to obtain the benzil class derivative through column.
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| WO2011071057A1 (en) * | 2009-12-09 | 2011-06-16 | 塩野義製薬株式会社 | Pharmaceutical composition for treatment or prevention of alzheimer's disease containing sulfur-containing heterocyclic derivative |
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